H-annellated benzo[f]chromenes

ABSTRACT

The present invention relates to specific photochromic h-annellated benzo[f]chromene derivatives and their use in synthetic resins of all types, especially for ophthalmic applications. In particular, the present invention relates to photochromic compounds derived from benzo[f]chromenes, which in the open form have especially long-wave absorption maxima making it possible to obtain violet to blue tints when used in phototropic glasses.

[0001] The present invention relates to specific photochromich-annellated benzo[f]chromene derivatives and their use in syntheticresins of all types, especially for ophthalmic applications. Inparticular, the present invention relates to photochromic compoundsderived from benzo[f]chromenes, which in their open form haveparticularly long-wave absorption maxima making it possible to achieveviolet to blue tints if used in phototropic glasses.

[0002] Various classes of dyes that reversibly change their color whenirradiated with light of certain wavelengths, particularly sunlight, areknown in the art. This is due to the fact that these dye moleculeschange into an excited colored state when supplied with energy in theform of light. When the energy supply is interrupted, they leave thisstate again and return to their colorless or at least hardly colorednormal state. These photochromic dyes include, for instance, thenaphthopyrans, which have already been described in the prior art withvarious substituents.

[0003] Pyrans, especially naphthopyrans and larger ring systems derivedtherefrom are photochromic compounds that even today are the subject ofintensive investigations. Although a patent application was filed forthem as early as 1966 (U.S. Pat. No. 3,567,605), it was not until thenineties that compounds that appeared suitable for use in eyeglasseswere developed.

[0004] On the one hand, the prior art dyes frequently do not havesufficiently long-wave absorption in the excited or in the unexcitedstate. This causes problems also in combinations with other photochromicdyes. On the other hand, they are also often excessively temperaturesensitive with respect to darkening and brightening is simultaneouslytoo slow. In addition, the described dyes have an insufficiently longservice life. Consequently, this type of sunglasses is not sufficientlydurable. The latter is noticeable in their rapidly deterioratingperformance and/or strong yellowing.

[0005] 3H-naphthopyrans derived from 2-naphthols and their higher analogderivatives derived therefrom by annellation are a group of photochromicdyes whose longest-wave absorption maximum in the excited form isprimarily in the spectral range of 420 nm to 500 nm. As a result theygive a yellow, orange or red color impression (see U.S. Pat. No.5,869,658 and U.S. Pat. No. 6,022,495). For neutrally darkeningphototropic glasses, however, powerful violet to blue photochromic dyesare required. Violet to blue photochromic dyes that are currentlyavailable in the prior art stem from the class of the spiroxazines,fulgides or 2H-naphtho[1,2-b]pyrans. Spiroxazine dyes, however, aretypically disadvantageous with respect to their high-temperatureperformance, while fulgide dyes do not have satisfactory properties foruse in sunglasses regarding their service life and2H-naphtho[1,2-b]pyrans regarding their brightening rate.

[0006] Thus, the object of the present invention is to provide novelphotochromic dyes with improved properties compared to the compoundsdescribed in the prior art. Compared to comparable prior art compounds,the photochromic compounds are to be distinguished especially bylonger-wave absorption in the excited state and at the same time are toexhibit good kinetic and service life properties, i.e., fasterbrightening rates and good behavior in the durability test.

[0007] This object is attained by the subjects characterized in theclaims.

[0008] Specifically provided are photochromic h-annellatedbenzo[f]chromenes having the general formula (I):

[0009] where

[0010] n and m independently represent 0, 1 or 2,

[0011] the radicals R₁, R₂, R₃ and R₄ each independently represent asubstituent selected from

[0012] the group α consisting of a hydrogen atom, a (C₁-C₆) alkylradical, a (C₃-C₇) cycloalkyl radical, which can have one or moreheteroatoms, a (C₁-C₆) alkoxy radical, a hydroxy group, atrifluoromethyl group, bromine, chlorine and fluorine;

[0013] the group β consisting of an unsubstituted, monosubstituted ordisubstituted phenyl, phenoxy, benzyl, benzyloxy, naphthyl or naphthoxyradical, wherein the substituents may be selected from the group a andphenyl;

[0014] the group χ wherein the radicals R₁ and R₂ or R₃ and R₄ each forman -A-(CH₂)_(k)—B— group bound to the aromatic ring where k=1 or 2,wherein A and B independently are selected from oxygen, sulfur, CH₂,C(CH₃)₂ or C(C₆H₅)₂, and wherein a benzo ring may in turn be annellatedto said -A-(CH₂)_(k)—B— group;

[0015] the group δ consisting of an unsubstituted, monosubstituted ordisubstituted amino group, wherein the amine substituents may beselected from a (C₁-C₆) alkyl radical, a (C₃-C₇) cycloalkyl radical, aphenyl or benzyl radical unsubstituted or substituted with one or moresubstituents from the group α, an N-morpholine group, anN-thiomorpholine group, an N-piperidine group, an N-azacycloheptanegroup, an N-piperazine group, an N-(N′-(C₁-C₆-alkyl)piperazine group, anN-pyrrolidine group, an N-imidazolidine group, an N-pyrazolidine group,an N-aziridine group, an N-azetidine group, an N-indoline group, anN-carbazole group, an N-phenothiazine group, an N-phenazine group, anN-phenoxazine group, an N-tetrahydroquinoline group, and anN-tetrahydroisoquinoline group,

[0016] the group ε, wherein the radicals R₁ and R₂, i.e., R₁/R₂, or R₃and R₄, i.e., R₃/R₄, respectively, together form a -D-(CH₂)_(k)-E- groupbound to the benzo ring where k=1 or 2, wherein independently D isselected from N(CH₃) or N(C₆H₅) and E from oxygen, sulfur, CH₂, C(CH₃)₂,C(C₆H₅)₂, N(CH₃) or N(C₆H₅), and wherein a benzo ring may in turn beannellated to this -D-(CH₂)_(k)-E- group, or

[0017] the group φ wherein the radicals R₁ and R₂ or R₃ and R₄,respectively, form a julolidinyl unit together with the benzene ring towhich they are bound,

[0018] provided that within the radicals R₁, R₂, R₃ and R₄ or withinR₁/R₂ and R₃/R₄ at least one is selected from the aforementioned groupsδ, ε and φ, i.e., at least one of the radicals R₁, R₂, R₃ and R₄ orR₁/R₂ and R₃/R₄ is an electron-donating substituent from the class ofthe nitrogen donor substituents;

[0019] the radicals R₅, R₆, R₇ and R₈, respectively, independently areselected from the group α and phenyl, or the radicals R₅ and R₆ togetherwith the radical R₃ of the directly adjacent benzo ring form anunsubstituted, monosubstituted or disubstituted benzo or pyrido ringannellated thereto, whose substituents may be selected from the group αand phenyl, or, if m or n is 2, the directly adjacent radicals R₅ and R₆of two adjacent CR₅R₆ units or the directly adjacent radicals R₇ and R₈of two adjacent CR₇R₈ units together form an annellated, unsubstituted,monosubstituted or disubstituted benzo or pyrido ring whose substituentsmay be selected from the group α and phenyl, or the radicals R₅ and R₆and/or the radicals R₇ and R₈ together represent a (C₃-C₇) cycloalkylradical, which can have one or more heteroatoms, such as, for instance,oxygen, nitrogen or sulfur, wherein a benzo ring may be annellated tothis cycloalkyl radical;

[0020] X is selected from O, S, CR₉R₁₀ or NR₁₁, wherein the radical R₁₁can be hydrogen, cyano, (C₁-C₆) alkyl, (C₃-C₇) cycloalkyl or phenyl, andthe radicals R₉ and R₁₀ independently are selected from the group α andphenyl, or the radicals R₉ and R₁₀ together represent a (C₃-C₇)cycloalkyl radical, which can have one or more heteroatoms, or, if X isCR₉R₁₀, the radicals R₉ and R₁₀ together with the radicals R₅ and R₆ orR₇ and R₈ of a directly adjacent CR₅R₆ unit or CR₇R₈ unit can also standfor an unsubstituted, monosubstituted or disubstituted benzo or pyridoring annellated to the X—C(R₅R₆) or X—C(R₇R₈) bond whose substituentsmay be selected from the group a and phenyl;

[0021] B and B′ independently are selected from one of the followinggroups a), b), c) or d), wherein they

[0022] a) are monosubstituted, disubstituted or trisubstituted arylradicals wherein the aryl radical is phenyl or naphthyl;

[0023] b) are unsubstituted, monosubstituted and disubstitutedheteroaryl radicals, wherein the heteroaryl radical is pyridyl, furanyl,benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothieno-2-yl,benzothieno-3-yl, or julolidinyl;

[0024]  wherein the substituents of the aryl or the heteroaryl radicalsin a) and b) are those selected from the groups α, β or δ or twodirectly adjacent substituents together can form a -D-(CH₂)_(k)-E- groupbound to the benzo ring as defined above, i.e., k stands for 1 or 2 andindependently D stands for —N(CH₃) or —N(C₆H₅) and E for oxygen, sulfur,CH₂, C(CH₃)₂, C(C₆H₅)₂, —N(CH₃) or —N(C₆H₅), and a benzo ring can inturn be annellated to this -D-(CH₂)_(k)-E- group;

[0025] c) are structural units having the following formulas (V) and(W):

[0026]  where

[0027] Y and Z independently are O, S, CH, CH₂ or NR₁₁, wherein theradical R₁₁ is as defined above, the radicals R₁₂ and R₁₃ independentlyrepresent hydrogen and/or a (C₁-C₆) alkyl radical and the radical R₁₄ isa substituent from the group α, wherein p is 1, 2, or 3, provided that,if Y in formula (V) is NR₁₁, Z is carbon, or

[0028] d) B and B′ together form an unsubstituted, monosubstituted ordisubstituted fluorene-9-ylidene radical or a saturated hydrocarbonradical, which is C₃-C₁₂ spiro-monocyclic, C₇-C₁₂ spiro-bicyclic and/orC₇-C₁₂ spiro-tricyclic wherein the fluorene substituents are selectedfrom the group α.

[0029] According to the present invention, through h-annellation ofbenzo[f]chromene systems, compounds are provided whose photochromicproperties have advantages compared to the compounds known in the priorart. In particular, the compounds according to the invention haveespecially long-wave absorption maxima in the open (colored) form, sothat for the first time violet to blue tints can be obtained forbenzo[f]chromene systems (nomenclature according to IUPAC; other name:3H-naphtho[1,2-b]pyrans). At the same time, the inventive photochromich-annellated benzo[f]chromene derivatives have comparable kinetic andservice life properties compared to corresponding compounds from theprior art, i.e., rapid brightening rate and good behavior in thedurability test.

[0030]FIG. 1 shows a synthesis pathway to prepare exemplary photochromiccompounds according to the invention.

[0031] The cycle or heterocycle annellated in the h-position of thebenzo[f]chromene system is preferably a five-membered ring (n=m=0), asix-membered ring (n=1, m=0 or m=1, n=0) or a seven-membered ring (withpreferably n=m=1).

[0032] Preferred photochromic h-annellated benzo[f]chromene derivativesaccording to the present invention have the following general formula(II) or (III):

[0033] where B, B′, R₁, R₂, R₃, R₄, R₇, R₈ and X are defined as above.

[0034] Preferably, the radicals R₁, R₂, R₃ and R₄ according to the aboveformulas (I), (II) or (III) are selected from the groups α, β and δ,provided that within the radicals R₁, R₂, R₃ and R₄ at least one isselected from the aforementioned group δ. Particularly preferably, atleast one of the radicals R₁ and R₂ is selected from the group δ.Particularly preferably at least one of the radicals R₁ and R₂ isselected from the group δ. Still more preferably, the radical R¹ isselected from the group δ, wherein the radical R₁ is bound in the7-position of the h-annellated 2H-benzo[f]chromene system. Within thegroup δ, an unsubstituted, monosubstituted or disubstituted amino groupis particularly preferred, wherein the amine substituents may beselected from a (C₁-C₆) alkyl radical, a (C₃-C₇) cycloalkyl radical, aphenyl or benzyl radical unsubstituted or substituted with one or moresubstituents of the group α, an N-morpholine group, an N-piperidinegroup, an N-azacycloheptane group, an N-piperazine group, anN-(N′-(C₁-C₆-alkyl) piperazine group, an N-pyrrolidine group, anN-imidazolidine group and an N-pyrazolidine group.

[0035] The radicals R₅, R₆, R₇ and R₈ each independently are selectedfrom preferably the group α. X can especially be O, CR₉R₁₀ or NR₁₁,wherein the radicals R₉, R₁₀ and R₁₁ are defined as above. If X standsfor CR₉R₁₀, the groups R₉ and R₁₀ together can especially stand for a(C₃-C₇) cycloalkyl radical, which can have one or more heteroatoms.

[0036] In a particularly preferred embodiment, B and B′ in the aboveformulas (I) or (II) and (III) independently are monosubstituted,disubstituted and trisubstituted aryl radicals, wherein the aryl radicalrespectively is a phenyl radical or a naphthyl radical.

[0037] If the radicals R₁ and R₂ or R₃ and R₄, respectively, form ajulolidinyl unit together with the benzene ring to which they are bound,i.e., with the benzo ring annellated in the f-position to the2H-chromene unit, the following structural unit results:

[0038] To be cited as the -A-(CH₂)_(k)—B— unit is especially—O—(CH₂)₂—O—, wherein a benzo cycle is possibly annellated to theethylene group thereof. To be cited as the -D-(CH₂)_(k)-E- unit are, inparticular: —NMe—(CH₂)₂—NMe—, —NPh—(CH₂)₂—NPh—, —NMe—(CH₂)₂—O—,NPh—(CH₂)₂—NMe—, and —NMe—(CH₂)₂—C(CH₃)₂—.

[0039] The -A-(CH₂)_(k)—B— unit or the -D-(CH₂)_(k)-E- unit is bound tothe respective benzo ring via A and B or D and E ortho to one another.

[0040] Particularly preferred photochromic h-annellated benzo[f]chromenederivatives according to the present invention are:

[0041] (1)7-dimethylamino-6-methoxy-2-(4-(N-morpholinyl)phenyl)-2-phenyl-2H,13H-indeno[1,2-h]benzo[f]chromene,

[0042] (2)7-dimethylamino-6-methoxy-2-(4-(N-morpholinyl)phenyl)-2,13,13-triphenyl-2H,13H-indeno[1,2-h]benzo[f]chromene,

[0043] (3)7-dimethylamino-6-methoxy-2-(4-(N-morpholinyl)phenyl)-2-phenyl-2H-13,14-dihydro-naphtho[1,2-h]benzo[f]chromene,

[0044] (4)7-dimethylamino-6-methoxy-2-(4-(N-morpholinyl)phenyl)-2-phenyl-2H-benzofuro[3,2-h]benzo[f]chromene,

[0045] (5)2-(4-dimethylaminophenyl)-6-methoxy-7-(N-piperidinyl)-2-phenyl-2H,13H-indeno[1,2-h]benzo[f]chromene,

[0046] (6)2-(4-dimethylaminophenyl)-6-methoxy-7-(N-piperidinyl)-2,13,13-triphenyl-2H,13H-indeno[1,2-h]benzo[f]chromene,

[0047] (7)2-(4-dimethylaminophenyl)-6-methoxy-7-(N-piperidinyl)-2-phenyl-2H-13,14-dihydro-naphtho[1,2-h]benzo[f]chromene,

[0048] (8)2-(4-dimethylaminophenyl)-6-methoxy-7-(N-piperidinyl)-2-phenyl-2H-benzofuro[3,2-h]benzo[f]chromene,

[0049] (9)2-(4-dimethylaminophenyl)-6-methoxy-7-(N-morpholinyl)-2-phenyl-2H,13H-indeno[1,2-h]benzo[f]chromene,

[0050] (10)2-(4-dimethylaminophenyl)-6-methoxy-7-(N-morpholinyl)-2,13,13-triphenyl-2H,13H-indeno[1,2-h]benzo[f]chromene,

[0051] (11)2-(4-dimethylaminophenyl)-6-methoxy-7-(N-morpholinyl)-2-phenyl-2H-13,14-dihydro-naphtho[1,2-h]benzo[f]chromene,

[0052] (12)2-(4-dimethylaminophenyl)-6-methoxy-7-(N-morpholinyl)-2-phenyl-2H-benzofuro[3,2-h]benzo[f]chromene,

[0053] (13)7-methoxy-6-(N-morpholinyl)-2-(4-(N-morpholinyl)phenyl)-2-phenyl-2H,13H-indeno[1,2-h]benzo[f]chromene,

[0054] (14)7-methoxy-6-(N-morpholinyl)-2-(4-(N-morpholinyl)phenyl)-2,13,13-triphenyl-2H,13H-indeno[1,2-h]benzo[f]chromene,

[0055] (15)7-methoxy-6-(N-morpholinyl)-2-(4-(N-morpholinyl)phenyl)-2-phenyl-2H-13,14-dihydro-naphtho[1,2-h]benzo[f]chromene,

[0056] (16)7-methoxy-6-(N-morpholinyl)-2-(4-(N-morpholinyl)phenyl)-2-phenyl-2H-benzofuro[3,2-h]benzo[f]chromene,

[0057] (17) 2-(4-dimethylaminophenyl)-9-methyl-2-phenyl-2H,9H, 15H-7,8-dihydroindeno[1,2-h]benzo[1,4]oxazino[6,7-f]chromene,

[0058] (18)2-(4-dimethylaminophenyl)-9-methyl-2,15,15-triphenyl-2H,9H,15H-7,8-dihydroindeno[1,2-h]benzo[1,4]oxazino[6,7-f]chromene,

[0059] (19)2-(4-dimethylaminophenyl)-9-methyl-2-phenyl-2H,9H-7,8,15,16-tetrahydronaphtho[1,2-h]benzo[1,4]oxazino[6,7-f]chromene,and

[0060] (20)2-(4-dimethylaminophenyl)-9-methyl-2-phenyl-2H,9H-benzofuro[3,2-h]benzo[1,4]-oxazino[6,7-f]chromene.

[0061] The longest-wave absorption maxima of the open form of theaforementioned exemplary photochromic h-annellated benzo[f]chromenederivatives according to the present invention are listed in thefollowing table by way of example. Longest-wave Absorption maximum ofthe Open Compounds (Colored) Form  (1) - (4) 570 - 575 nm  (5) - (8)585 - 595 nm  (9) - (12) 565 - 575 nm (13) - (16) 545 - 555 nm (17) -(20) 590 - 600 nm

[0062] The compounds according to the invention can be used in syntheticresin materials or synthetic resin objects of any type and shape for awide variety of applications where photochromic behavior is important.It is possible to use one dye according to the present invention or amixture of such dyes. For example, the inventive photochromicbenzo[f]chromene dyes may be used in lenses, particularly ophthalmiclenses, lenses for eyeglasses of all types, e.g., ski goggles,sunglasses, motor cycle goggles, visors for protective helmets and thelike. The inventive photochromic benzo[f]chromene dyes may also be usedas sun protection in vehicles and living spaces in the form of windows,protective baffles, covers, roofs, or the like.

[0063] To produce such photochromic objects, the inventive photochromicbenzo[f]chromene dyes may be applied to or embedded in a polymermaterial, such as an organic synthetic resin material, by variousmethods described in the prior art, for instance in WO 99/15518.

[0064] A distinction is drawn between so-called mass dyeing andsuperficial dyeing processes. A mass dyeing process comprises, forinstance, dissolving or dispersing of the photochromic compound orcompounds according to the present invention in a synthetic resinmaterial, e.g., by adding the photochromic compound(s) to a monomermaterial before polymerization takes place. Another option to produce aphotochromic object is to allow the photochromic compound(s) topenetrate the synthetic resin material(s) by dipping the synthetic resinmaterial into a hot solution of the photochromic dye(s) according to thepresent invention or, for instance, to use a thermotransfer process. Thephotochromic compound(s) can, for instance, also be provided in the formof a separate layer between adjacent layers of the synthetic resinmaterial, e.g., as part of a polymer film. It is also possible to applythe photochromic compound(s) as part of a coating that is applied to thesurface of the synthetic resin material. The term “penetration” shouldbe understood as the migration of the photochromic compound(s) into thesynthetic resin material, e.g., by the solvent-supported transfer of thephotochromic compound(s) into a polymer matrix, vapor phase transfer orother similar surface diffusion processes.

[0065] Advantageously, such photochromic objects, e.g., eyeglasses, canbe produced not only by means of the usual mass dyeing process but alsoby means of superficial dyeing. In the latter variant, a surprisinglylow migration tendency can be achieved. This is advantageousparticularly in subsequent processing steps since, for instance, in anantireflective coating, film peeling and similar defects can bedrastically reduced due to the reduced back diffusion in the vacuum.

[0066] Overall, based on the inventive photochromic h-annellatedbenzo[f]chromene derivatives, any compatible (compatible in chemicalrespects as well as in color) colorations, i.e., dyes, can be applied toor embedded in the synthetic resin material to satisfy both estheticconsiderations as well as medical or fashion aspects. The specificallyselected dye(s) can consequently vary as a function of the intendedeffects and requirements.

[0067] The inventive photochromic h-annellated benzo[f]chromenederivatives having the general formula (I) or (II) and (III) can, forinstance, be produced using the reaction scheme shown in FIG. 1.

[0068] Starting with suitably substituted phenyl acetic acid esters, anester condensation with cyclic aromatic-aliphatic ketones is carried outusing potassium methylate as base (see step i) in FIG. 1). Thesubstituted cyclic aromatic-aliphatic 2-phenylacetyl ketones obtained instep i) are subsequently converted to substituted annellated 2-naphtholderivatives in step ii) in an intramolecular cyclization by means ofphosphoric acid. After protecting the naphthol hydroxy group astert-butyl diphenylsilyl ether (step iii)), the (substituted) aminogroup required for long-wave absorption is introduced on the naphthalenesystem by means of palladium catalyzed amination (step iv)). Thestarting compounds required for this in step iv) carry either a bromineatom or a triflate group as radicals R₁ or R₂, which may either bepresent from the start, i.e., in the phenyl acetic acid ester used asstarting material in step i), or may be conventionally introduced priorto amination. After splitting off the protective silyl ether group instep v), the substituted annellated 2-naphthol derivatives thus obtainedare converted into the inventive compounds with suitable substituted2-propyne-1-ol derivatives in accordance with step vi).

1. Photochromic h-annellated benzo[f]chromenes having the generalformula (I):

where n and m independently represent 0, 1 or 2, the radicals R₁, R₂, R₃and R₄ each independently represent a substituent selected from thegroup α consisting of a hydrogen atom, a (C₁-C₆) alkyl radical, a(C₃-C₇) cycloalkyl radical, which can have one or more heteroatoms, a(C₁-C₆) alkoxy radical, a hydroxy group, a trifluoromethyl group,bromine, chlorine and fluorine; the group β consisting of anunsubstituted, monosubstituted or disubstituted phenyl, phenoxy, benzyl,benzyloxy, naphthyl or naphthoxy radical, wherein the substituents maybe selected from the group a and phenyl; the group χ wherein theradicals R₁ and R₂ or R₃ and R₄, each form an -A-(CH₂)_(k)-B- groupbound to the aromatic ring where k=1 or 2, wherein A and B independentlyare selected from oxygen, sulfur, CH₂, C(CH₃)₂ or C(C₆H₅)₂, and whereina benzo ring can in turn be annellated to said -A-(CH₂)_(k)-B- group;the group δ consisting of an unsubstituted, monosubstituted ordisubstituted amino group, wherein the amine substituents may beselected from a (C₁-C₆) alkyl radical, a (C₃-C₇) cycloalkyl radical, aphenyl or benzyl radical unsubstituted or substituted with one or moresubstituents from the group α, an N-morpholine group, anN-thiomorpholine group, an N-piperidine group, an N-azacycloheptanegroup, an N-piperazine group, an N-(N′-(C₁-C₆-alkyl)piperazine group, anN-pyrrolidine group, an N-imidazolidine group, an N-pyrazolidine group,an N-aziridine group, an N-azetidine group, an N-indoline group, anN-carbazole group, an N-phenothiazine group, an N-phenazine group, anN-phenoxazine group, an N-tetrahydroquinoline group, and anN-tetrahydroisoquinoline group, the group ε, wherein the radicals R₁ andR₂, or R₃ and R₄, respectively, together form a -D-(CH₂)_(k)-E- groupbound to the benzo ring where k=1 or 2, wherein independently D isselected from N(CH₃) or N(C₆H₅) and E from oxygen, sulfur, CH₂, C(CH₃)₂,C(C₆H₅)₂, N(CH₃) or N(C₆H₅), and wherein a benzo ring may in turn beannellated to this -D-(CH₂)_(k)-E- group, or the group φ wherein theradicals R₁ and R₂ or R₃ and R₄, respectively, form a julolidinyl unittogether with the benzene ring to which they are bound, provided thatwithin the radicals R₁, R₂ R₃ and R₄ or within R₁/R₂ and R₃/R₄ at leastone is selected from the aforementioned groups δ, ε and φ, the radicalsR₅, R₆, R₇ and R₈ each independently are selected from the group α andphenyl, or the radicals R₅ and R₆ together with the radical R₃ of thedirectly adjacent benzo ring form an unsubstituted, monosubstituted ordisubstituted benzo or pyrido ring annellated thereto, whosesubstituents may be selected from the group α and phenyl, or, if m or nis 2, the directly adjacent radicals R₅ and R₆ of two adjacent CR₅R₆units or the directly adjacent radicals R₇ and R₈ of two adjacent CR₇R₈units together form an annellated, unsubstituted, monosubstituted ordisubstituted benzo or pyrido ring whose substituents may be selectedfrom the group α and phenyl, or the radicals R₅ and R₆ and/or theradicals R₇ and R₈ together represent a (C₃-C₇) cycloalkyl radical,which can have one or more heteroatoms, wherein a benzo ring may beannellated to this cycloalkyl radical; X is selected from O, S, CR₉R₁₀or NR₁₁, wherein the radical R₁₁ can be hydrogen, cyano, (C₁-C₆) alkyl,(C₃-C₇) cycloalkyl or phenyl, and the radicals R₉ and R₁₀ independentlyare selected from the group α and phenyl, or the radicals R₉ and R₁₀together represent a (C₃-C₇) cycloalkyl radical, which can have one ormore heteroatoms, or, if X is CR₉R₁₀, the radicals R₉ and R₁₀ togetherwith the radicals R₅ and R₆ or R₇ and R₈ of a directly adjacent CR₅R₆group or CR₇R₈ unit can also stand for an unsubstituted, monosubstitutedor disubstituted benzo or pyrido ring annellated to the X—C(R₅R₆) orX—C(R₇R₈) bond whose substituents may be selected from the group α andphenyl; B and B′ independently are selected from one of the followinggroups a), b), c) or d), wherein they a) are monosubstituted,disubstituted or trisubstituted aryl radicals wherein the aryl radicalis phenyl or naphthyl; b) are unsubstituted, monosubstituted anddisubstituted heteroaryl radicals, wherein the heteroaryl radical ispyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl,benzothieno-2-yl, benzothieno-3-yl, or julolidinyl;  wherein thesubstituents of the aryl or the heteroaryl radicals in a) and b) arethose selected from the groups α, β or δ or two directly adjacentsubstituents together can form a -D-(CH₂)_(k)-E- group bound to thebenzo ring as defined above, c) are structural units having thefollowing formulas (V) and (W):

 where Y and Z independently are O, S, CH, CH₂ or NR₁₁, wherein theradical R₁₁ is as defined above, the radicals R₁₂ and R₁₃ independentlyrepresent hydrogen and/or a (C₁-C₅) alkyl radical and the radical R₁₄ isa substituent from the group α, where p is 1, 2, or 3, provided that, ifY in formula (V) is NR₁₁, Z is carbon, or d) B and B′ together form anunsubstituted, monosubstituted or disubstituted fluorene-9-ylideneradical or a saturated hydrocarbon radical, which is C₃-C₁₂spiro-monocyclic, C₇-C₁₂ spiro-bicyclic and/or C₇-C₁₂ spiro-tricyclic,wherein the fluorene substituents are selected from the group α. 2.Photochromic benzo[f]chromenes as claimed in claim 1, wherein the cycleor heterocycle annellated according to formula (I) in the h-position ofthe benzo[f]chromene system is a five-membered ring, a six-membered ringor a seven-membered ring.
 3. Photochromic benzo[f]chromenes as claimedin claim 1 or 2 having the following general formula (II) or (III):

where B, B′, R₁, R₂, R₃, R₄, R₇, R₈ and X are defined as above. 4.Photochromic benzo[f]chromenes as claimed in any one of claims 1 to 3,wherein the radicals R₁, R₂ R₃ and R₄ are selected from the groups α, β,and δ, provided that within the radicals R₁, R₂, R₃ and R₄ at least oneis selected from the aforementioned group δ.
 5. Photochromicbenzo[f]chromenes as claimed in claim 4, wherein at least one of theradicals R₁ and R₂ is selected from the group δ.
 6. Photochromicbenzo[f]chromenes as claimed in claim 5, wherein the radical R₁ isselected from the group δ and is bound in the 7-position of theh-annellated 2H-benzo[f]chromene system.
 7. Photochromicbenzo[f]chromenes as claimed in any one of claims 1 to 6, wherein thesubstituent from the group δ is an unsubstituted, monosubstituted ordisubstituted amino group, wherein the amine substituents may beselected from a (C₁-C₆) alkyl radical, a (C₃-C₇) cycloalkyl radical, aphenyl or benzyl radical unsubstituted or substituted with one or moresubstituents from the group α, an N-morpholine group, an N-piperidinegroup, an N-azacycloheptane group, an N-piperazine group, anN-(N′-(C₁-C₆-alkyl)piperazine group, an N-pyrrolidine group, anN-imidazolidine group or an N-pyrazolidine group.
 8. Photochromicbenzo[f]chromenes as claimed in any one of claims 1 to 7, wherein theradicals R₅, R₆, R₇ and R₈ each independently are selected from thegroup α.
 9. Photochromic benzo[f]chromenes as claimed in any one ofclaims 1 to 8, wherein X is O, CR₉R₁₀ or NR₁₁, wherein the radicals R₉,R₁₀ and R₁₁ are defined as above.
 10. Photochromic benzo[f]chromenes asclaimed in any one of the preceding claims, which are7-dimethylamino-6-methoxy-2-(4-(N-morpholinyl)phenyl)-2-phenyl-2H,13H-indeno[1,2-h]benzo[f]chromene,7-dimethylamino-6-methoxy-2-(4-(N-morpholinyl)phenyl)-2,13,13-triphenyl-2H,13H-indeno[1,2-h]benzo[f]chromene,7-dimethylamino-6-methoxy-2-(4-(N-morpholinyl)phenyl)-2-phenyl-2H-13,14-dihydro-naphtho[1,2-h]benzo[f]chromene,7-dimethylamino-6-methoxy-2-(4-(N-morpholinyl)phenyl)-2-phenyl-2H-benzofuro[3,2-h]benzo[f]chromene,2-(4-dimethylaminophenyl)-6-methoxy-7-(N-piperidinyl)-2-phenyl-2H,13H-indeno[1,2-h]benzo[f]chromene,2-(4-dimethylaminophenyl)-6-methoxy-7-(N-piperidinyl)-2,13,13-triphenyl-2H,13H-indeno[1,2-h]benzo[f]chromene,2-(4-dimethylaminophenyl)-6-methoxy-7-(N-piperidinyl)-2-phenyl-2H-13,14-dihydro-naphtho[1,2-h]benzo[f]chromene,2-(4-dimethylaminophenyl)-6-methoxy-7-(N-piperidinyl)-2-phenyl-2H-benzofuro[3,2-h]benzo[f]chromene,2-(4-dimethylaminophenyl)-6-methoxy-7-(N-morpholinyl)-2-phenyl-2H,13H-indeno[1,2-h]benzo[f]chromene,2-(4-dimethylaminophenyl)-6-methoxy-7-(N-morpholinyl)-2,13,13-triphenyl-2H,13H-indeno[1,2-h]benzo[f]chromene,2-(4-dimethylaminophenyl)-6-methoxy-7-(N-morpholinyl)-2-phenyl-2H-13,14-dihydro-naphtho[1,2-h]benzo[f]chromene,2-(4-dimethylaminophenyl)-6-methoxy-7-(N-morpholinyl)-2-phenyl-2H-benzofuro[3,2-h]benzo[f]chromene,7-methoxy-6-(N-morpholinyl)-2-(4-(N-morpholinyl)phenyl)-2-phenyl-2H,13H-indeno[1,2-h]benzo[f]chromene,7-methoxy-6-(N-morpholinyl)-2-(4-(N-morpholinyl)phenyl)-2,13,13-triphenyl-2H,13H-indeno[1,2-h]benzo[f]chromene,7-methoxy-6-(N-morpholinyl)-2-(4-(N-morpholinyl)phenyl)-2-phenyl-2H-13,14-dihydro-naphtho[1,2-h]benzo[f]chromene,7-methoxy-6-(N-morpholinyl)-2-(4-(N-morpholinyl)phenyl)-2-phenyl-2H-benzofuro[3,2-h]benzo[f]chromene,2-(4-dimethylaminophenyl)-9-methyl-2-phenyl-2H,9H,15H-7,8-dihydroindeno[1,2-h]benzo[1,4]oxazino[6,7-f]chromene,2-(4-dimethylaminophenyl)-9-methyl-2,15,15-triphenyl-2H,9H,15H-7,8-dihydroindeno[1,2-h]benzo[1,4]oxazino[6,7-f]chromene,2-(4-dimethylaminophenyl)-9-methyl-2-phenyl-2H,9H-7,8,15,16-tetrahydronaphtho[1,2-h]benzo[1,4]oxazino[6,7-f]chromene,and2-(4-dimethylaminophenyl)-9-methyl-2-phenyl-2H,9H-benzofuro[3,2-h]benzo[1,4]-oxazino[6,7-f]chromene.11. Use of the photochromic benzo[f]chromenes as claimed in any one ofclaims 1 to 10 in synthetic resin materials.
 12. Use as claimed in claim11, wherein the synthetic resin material is an ophthalmic lens.